Methods of making and using freestanding reactive multilayer foils

ABSTRACT

Reactive foils and their uses are provided as localized heat sources useful, for example, in ignition, joining and propulsion. An improved reactive foil is preferably a freestanding multilayered foil structure made up of alternating layers selected from materials that will react with one another in an exothermic and self-propagating reaction. Upon reacting, this foil supplies highly localized heat energy that may be applied, for example, to joining layers, or directly to bulk materials that are to be joined. This foil heat-source allows rapid bonding to occur at room temperature in virtually any environment (e.g., air, vacuum, water, etc.). If a joining material is used, the foil reaction will supply enough heat to melt or soften the joining material, which upon cooling will form a strong bond, joining two or more bulk materials. If no joining material is used, the foil reaction supplies heat directly to at least two bulk materials, melting or softening a portion of each bulk, which upon cooling, form a strong bond. Additionally, the foil may be designed with openings that allow extrusion of the joining (or bulk) material through the foil to enhance bonding.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of three U.S. patentapplications (hereinafter “the parent applications”): 1) U.S.application Ser. No. 09/846,486 filed by T. P. Weihs et al. on May 1,2001 now U.S. Pat. No. 6,736,942 and entitled “Freestanding ReactiveMultilayer Foils”; 2) U.S. application Ser. No. 09/846,422 filed by T.P. Weihs et al. on May 1, 2001 now abandoned and entitled “ReactiveMultilayer Structures For Ease of Processing and Enhanced Ductility”;and 3) U.S. application Ser. No. 09/846,447 filed by T. P. Weihs et al.on May 1, 2001 now U.S. Pat. No. 6,534,194 and entitled “Method ofMaking Reactive Multilayer Foil and Resulting Product.” Each of thethree parent applications claims the benefit of U.S. ProvisionalApplication Ser. No. 60/201,292 filed by T. P. Weihs et al. on May 2,2000 and entitled “Reactive Multilayer Foils.” The three parentapplications and the '292 provisional application are incorporatedherein by reference.

This application also claims the benefit of U.S. Provisional ApplicationSer. No. 60/362,976 filed by T. P. Weihs et al. on Mar. 8, 2002 andentitled “Freestanding Reactive Multilayer Foils.” The '976 provisionalapplication is also incorporated herein by reference.

GOVERNMENT INTEREST

This invention was made with government support under NSF Grant Nos.DMR-9702546 and DMR-9632526 and The Army Research Lab/Advanced MaterialsCharacterization Program through Award No. 019620047. The government hascertain rights in the invention.

FIELD OF THE INVENTION

This invention relates to reactive multilayer foils, especiallyfreestanding multilayer foils, useful as local heat sources.

BACKGROUND OF THE INVENTION

Reactive multilayer coatings are useful in a wide variety ofapplications requiring the generation of intense, controlled amounts ofheat in a planar region. Such structures conventionally comprise asuccession of substrate-supported coatings that, upon appropriateexcitation, undergo an exothermic chemical reaction that spreads acrossthe area covered by the layers generating precisely controlled amountsof heat. While we will describe these reactive coatings primarily assources of heat for welding, soldering or brazing, they can also be usedin other applications requiring controlled local generation of heat suchas propulsion and ignition.

In many methods of bonding or joining materials, a heat source isrequired. This heat source may either be external or internal to thestructure to be joined. When external, the heat may be generated from adevice such as a furnace. Processes incorporating such heat sourcesrequire the heating of the entire unit to be bonded, including the bulkmaterials and the bond material, to a temperature high enough to meltthe bond material. Such a method presents problems because the bulkmaterials to be joined are often delicate or sensitive to the hightemperatures required in the process. These high temperatures may damagethe materials to be bonded.

To alleviate the problems associated with external heat sources,internal heat sources are utilized. These heat sources often take theform of reactive powders or even electrical wires. When reactive powdersare used, a mixture of metals or compounds that will reactexothermically in a self-propagating reaction to form a final compoundor alloy is utilized. Such processes have existed since self-propagatingpowders were developed in the early 1960s, spawning what is known asSelf-Propagating, High-Temperature Synthesis (SHS). SHS reactions,however, often require substantial preheating to self-propagate, andcontrolling the rate and manner in which their energy is released isoften difficult. As a result, bonding may be inconsistent orinsufficient.

To combat the problems associated with reactive powder bonding,multilayer structures comprised of materials, which allow similarexothermic reactions, have been developed. Such structures allow formore controllable and consistent heat generating reactions. The basicdriving force behind such SHS reactions is a reduction in atomic bondenergy. When a structure having a series of layers of reactive material(known as a foil) is ignited, heat is produced as the distinct layersatomically combine. This heat ignites adjacent regions of the foil,thereby allowing the reaction to travel the entire length of thestructure, generating heat until all material is reacted. Even with suchadvances in bonding technology, however, there remain problems. Manymaterials, for example, posed major difficulties and previously couldnot be successfully bonded. Additionally, methods utilizing reactivefoils as heat sources often resulted in the foil debonding from thesubstrate upon reaction, thereby weakening the bond. Accordingly thereis a need for improved reactive multilayer foils.

SUMMARY OF THE INVENTION

Reactive foils and their uses are provided as localized heat sourcesuseful, for example, in ignition, joining and propulsion. An improvedreactive foil is preferably a freestanding multilayered foil structuremade up of alternating layers selected from materials that will reactwith one another in an exothermic and self-propagating reaction. Uponreacting, this foil supplies highly localized heat energy that may beapplied, for example, to joining layers, or directly to bulk materialsthat are to be joined. This foil heat-source allows rapid bonding tooccur at room temperature in virtually any environment (e.g., air,vacuum, water, etc.). If a joining material is used, the foil reactionwill supply enough heat to melt or soften the joining material, whichupon cooling will form a strong bond, joining two or more bulkmaterials. If no joining material is used, the foil reaction suppliesheat directly to at least two bulk materials, melting or softening aportion of each bulk, which upon cooling, form a strong bond.Additionally, the foil may be designed with openings that allowextrusion of the joining (or bulk) material through the foil to enhancebonding.

BRIEF DESCRIPTION OF THE DRAWINGS

Many advantages, features, and applications of the invention will beapparent from the following detailed description of preferredembodiments of the invention, which is provided in connection with theaccompanying drawings. In the drawings:

FIG. 1 illustrates an exemplary multilayer reactive foil duringreaction;

FIG. 2 shows the freestanding elements of an exemplary joiningapplication;

FIG. 3 illustrates initiation of a joining application;

FIG. 4 shows an exemplary perforated reactive foil;

FIG. 5 depicts the flow of joining material through holes in a foil;

FIG. 6 illustrates formation of a reactive foil by cold rolling;

FIG. 7 is a schematic cross section of a composite reactive foilcomposed of sets of microlaminate foils and nanolaminate foils;

FIG. 8 shows the use of reactive foil to join a semiconductor ormicroelectronic device to a substrate; and

FIGS. 9A and 9B illustrate a patterned reactive foil wherein someregions react to form conductive regions and others form non-conductiveregions.

It is to be understood that these drawings are for the purpose ofillustrating the concepts of the invention and are not to scale.

DETAILED DESCRIPTION

Preferred embodiments and applications of the invention will now bedescribed. Other embodiments may be realized and compositional orstructural changes may be made without departing from the spirit orscope of the invention. Although the embodiments disclosed herein havebeen particularly described as joining or bonding bulk materialsutilizing a freestanding, self-propagating reactive foil structure, itshould be readily apparent that the invention may be embodied for otheruses or applications requiring an intense localized heat source.

In accordance with a preferred embodiment of the invention, a multilayerreactive structure (generically referred to herein as a “foil”) isprovided as a local heat source in a variety of applications such as aprocess for joining two or more (of the same or different) materialstogether. As illustrated in FIG. 1, reactive multilayer foil 14 is madeup of alternating layers 16 and 18 of materials A and B, respectively.These alternating layers 16 and 18 may be any materials amenable tomixing of neighboring atoms (or having changes in chemical bonding) inresponse to a stimulus, including suicides (e.g., Rh/Si, Ni/Si, andZr/Si, etc.), aluminides (e.g., Ni/Al, Ti/Al, Monel/Al, and Zr/Al,etc.), borides (e.g. Ti/B), carbides (e.g., Ti/C), thermite reactingcompounds (e.g., Al/Fe₂O₃ or Al/Cu₂O), alloys, metallic glasses, andcomposites (e.g., metal ceramic).

The materials (A/B) used in fabrication of the reactive foil arepreferably chemically distinct. In a preferred embodiment, layers 16, 18alternate between a transition metal (e.g., Ti, Ni, etc.) and a lightelement (e.g., B, Al, etc.). Preferably, the pairs (A/B) of elements arechosen based on the way they react to form stable compounds with largenegative heats of formation and high adiabatic reaction temperatures, asdescribed in T. P. Weihs, “Self-Propagating Reactions in MultilayerMaterials,” Handbook of Thin Film Process Technology, 1997, which isincorporated herein by reference in its entirety. In a preferredembodiment, at least one of the layers of the reactive foil is (orcontains) Al.

When a multilayer foil 14 is exposed to a stimulus (e.g., spark, energypulse, etc.), for example at one end, neighboring atoms from materials Aand B mix, e.g. as shown in region 30. The change in chemical bondingcaused by this mixing results in a reduction in atomic bond energy, thusgenerating heat in an exothermic chemical reaction. This change inchemical bonding occurs as layers with A-A bonds (i.e., layer 16) andlayers with B-B bonds (i.e., layer 18) are exchanged for A-B bonds,thereby reducing the chemical energy stored in each layer, andgenerating heat. As FIG. 1 further illustrates, this generated heatdiffuses through foil 14 (in a direction from reacted section 30 throughreaction zone 32 to unreacted section 34) and initiates additionalmixing of the unreacted layers. As a result, a self-sustaining/selfpropagating reaction (SHS reaction) is produced through foil 14. Withsufficiently large and rapid heat generation, the reaction propagatesacross the entire foil 14 at velocities typically greater than 1 m/s. Asthe reaction does not require additional atoms from the surroundingenvironment (as, for example, oxygen in the case of combustion), thereaction makes foil 14 a self-contained source of energy capable ofemitting bursts of heat and light rapidly, reaching temperatures above1400 K, and a local heating rate reaching 10⁹ K/s. This energy isparticularly useful in applications (e.g., joining, ignition, etc.)requiring production of heat rapidly and locally.

When a reaction propagates across a multilayer foil 14 as illustrated byFIG. 1, the maximum temperature of the reaction is typically located atthe trailing edge of the reaction zone 32. This may be considered thefinal temperature of reaction, which can be determined by the heat ofreaction (ΔH_(rx)), the heat lost to the environment or surroundingmaterial (ΔH_(env)), the average heat capacity of the sample (C_(p)),and the mass of the sample, M. Another factor in determining the finaltemperature is whether or not the reaction temperature exceeds themelting point of the final product. If the melting point is exceeded,then some heat is absorbed in the state transformation from solid toliquid of the product. The final temperature of reaction may bedetermined using the following formulas (where T_(o) is the initialtemperature, ΔH_(m) is the enthalpy of melting, T_(m) is the meltingtemperature of the product, and there is no reaction with thesurrounding environment or material), depending upon whether finalproduct melting occurs:T _(f) =T _(o)−(ΔH _(rx) +ΔH _(env))/(C _(p) M) If no melting of finalproduct occurs;T_(f)=T_(m) If there is a two-phase region of solid and liquid finalproduct; andT _(f) =T _(o)−(ΔH _(rx) +ΔH _(env) +ΔH _(m))/(C _(p) M) If the finalproduct completely melts.

Intricately related to the heat of the foil reaction is the velocity ofthe propagation of the reaction along the length of foil 14. The speedat which the reaction can propagate depends on how rapidly the atomsdiffuse normal to their layering (FIG. 1) and how rapidly heat isconducted along the length of foil 14. The propagation velocity is astrong function of the thicknesses of the individual layers in themultilayer foil. As the thickness of individual layers 16, 18 decreases,the diffusion distances are smaller and atoms can mix more rapidly. Heatis released at a higher rate, and therefore the reaction travels fasterthrough the foil structure.

In accordance with a preferred embodiment of the invention, reactivemultilayer foils 14 may be fabricated by physical vapor deposition (PVD)methods. A magnetron sputtering technique, for example, may be used todeposit the materials A/B on a substrate (shown in FIG. 1 in dashedoutline form as layer 35) as alternating layers 16, 18. Substrate 35 maybe rotated over two sputter guns in a manner well known in the art toeffectuate the layering of materials A/B into alternating layers 16, 18.

Substrate 35 is shown in dashed outline form to indicate that it is aremovable layer that facilitates fabrication of the reactive foil 14 asa freestanding foil. Substrate 35 may be any substrate (e.g., Si, glass,or other underlayer) having the characteristics of providing sufficientadhesion so as to keep the foil layers on the substrate duringdeposition, but not too adhesive to prevent the foil from being removedfrom the substrate following deposition. The substrate can include acoating of release material or adhesion material to fine tune itsadhesion characteristics.

Advantageously an additional wetting layer (e.g., tin) may be used as aninterface layer between the first layer of foil (16 or 18) and thesubstrate 35 to provide the necessary adhesive. When no wetting layer isemployed, selection of the appropriate material A/B as the first layerdeposited on the substrate will ensure that the necessary adhesiverequirements are met. When a reactive foil using Al/Monel as materialsA/B is to be fabricated, for example, without a wetting layer, theexemplary reactive foil would be deposited on a substrate such as Siwith the first layer being Al deposited on the substrate. Al ispreferably selected as the first layer in such case because Al willsufficiently adhere to Si during depositing, but will allow peeling offof the substrate after the foil is formed.

A fabricated foil 14 may have hundreds to thousands of alternatinglayers 16 and 18 stacked on one another. Individual layers 16 and 18preferably have a thickness ranging from 1–1000 nm. In a preferredembodiment, the total thickness of foil 14 may range from 10 μm to 1 cm.

Another method of fabricating is to deposit material in a codepositiongeometry. Using this method, both material sources are directed onto onesubstrate and the atomic fluxes from each material source are shutteredto deposit the alternate layers 16 and 18. An alternative method is toeliminate shuttering altogether and rotate substrates over two materialsources that have physically distinct atomic fluxes. With this method,each pass over a source preferably generates an individual layer.

Preferably the degree of atomic intermixing of materials A/B that mayoccur during deposition should be minimized. This may be accomplished bydepositing the multilayers onto cooled substrates, particularly whenmultilayers 16 and 18 are sputter deposited. To the extent that somedegree of intermixing is unavoidable, a relatively thin (as compared tothe alternating unreacted layers) region of pre-reacted material 20 willbe formed. Such a pre-reacted region 20, nevertheless, is helpful inthat it serves to prevent further and spontaneous reaction in foil 14.

In an alternative embodiment, a multilayer reactive foil may befabricated using mechanical techniques such as repeated rolling oflayered composites.

As illustrated in FIG. 1, the preferred reactive foil 14 is afreestanding multilayer reactive foil for particular use as aheat-generating source. Freestanding foils are easier to characterizethan thin films because they can be handled like “bulk” samples. Makingreactive foils 14 freestanding greatly expands their possible uses.Because such reactive foils are not necessarily associated with anyparticular application, they may be mass-produced for any purposerequiring a self-propagating localized heat source. Their production isnot limited or impeded by placing large or delicate items into a vacuumchamber to be coated by a reactive multilayer foil. Moreover,freestanding foils will allow heat sinking to the substrate to beminimized where unwanted.

Freestanding foils in accordance with preferred embodiments of theinvention may be adapted for use in a variety of applications. Forexample, the freestanding foils may be used to couple bodies ofmaterials (referred to herein as “bulk materials”) together to form aunified product. Freestanding foils may find use in any number ofbonding, soldering, brazing, welding or other applications to join bulkmaterials. A typical joining application is represented in FIG. 3, inwhich two or more bulk materials 10 are to be joined together. The bulkmaterials 10 may be ceramics, metallic glasses, metals/alloys, polymers,composites, semiconductors, and other forms of material.

In the particular joining application illustrated in FIG. 3, joiningmaterial 12 is used to join bulk materials 10 together. Joining material12 may be any layer (or composite layer) of material to be softened ormelted to join bulk materials 10 together. Joining material 12 can be inthe form of freestanding sheets made up of metallic glasses,metals/alloys, functionally graded layers, Ni—B films, solder, brazes,self-propagating braze, combinations of such, or other like joiningmaterials.

In accordance with a preferred embodiment of the invention, a reactivefoil 14 is positioned between joining materials 12 to form a structuresomewhat like a sandwich. The reactive foil “sandwich” thus formed ispreferably positioned between bulk materials 10 at the location (e.g.,end point, joint, intersection, etc.) at which the bulk materials 10 areto be joined together.

Alternatively, a reactive foil 14 is positioned between bulk materials10 which have previously been coated with joining materials 12.

The joining process involves the application of force (as symbolicallyrepresented by vice 11 in FIG. 3) to maintain the relative positions ofbulk materials 10, joining materials 12, and reactive foil 14.Advantageously all components are freestanding elements pressedtogether. In an alternative embodiment, joining materials 12 are pressedas a composite with reactive foil 14.

Once the components of the joining process are positioned, a stimulus(shown as lighted match 15) is applied, preferably, to one end ofreactive foil 14 to initiate an SHS reaction. The intermixing of atomswithin reactive foil 14 produces rapid and intense heat sufficient tosoften or melt joining materials 12 along the entire length of reactivefoil 14. In this state, joining materials 12 are sufficient to join bulkmaterials 10 together. Shortly thereafter, the joined materials 10return to the temperature of the environment (e.g., room temperature)and can be removed from the applied force (graphically represented byvice 11).

A composite structure composed of joining materials 12 and reactive foil14 can be formed through deposition (e.g., vapor depositing) of reactivefoil 14 onto one layer of joining material 12. Another layer of joiningmaterial is then combined with reactive foil 14 through vapor depositionor an application of force (e.g., cold rolling).

Advantageously a wetting/adhesion layer may be added to facilitatesurface wetting for the reactive foil 14, bulk materials 10, or both.The wetting/adhesion layer allows uniform spreading of joining materialto ensure consistent joining of bulk materials. The wetting/adhesionlayer may be a thin layer of joining material (e.g., braze), Ti, Sn,metallic glass, etc. Commercial alloys such as Ag—Sn, Ag—Cu—Ti, Cu—Ti,Au—Sn, and Ni—B may also be used.

Preferred embodiments of the invention are useable as freestandingreactive foils 14 with increased total thickness. The total thickness ofsuch a reactive foil depends upon the thickness and number of theelemental layers (e.g., 16 and 18) utilized to form the foils. Foilsthat are less than 10 μm are very hard to handle as they tend to curl upon themselves. Foils on the order of 100 μm are stiff, and thus, easilyhandled. Thicker foils also minimize the risk of a self-propagatingreaction being quenched in the foils. In joining applications usingreactive foils, there is a critical balance between the rate at whichthe foil generates heat and the rate at which that heat is conductedinto the surrounding braze layers and the joint to be formed. If heat isconducted away faster than it is generated, the reaction will bequenched and the joint cannot be formed. The thicker foils make itharder to quench the reaction because there is a larger volumegenerating heat and the same surface area through which heat is lost.

Thicker foils can be utilized with reaction temperatures that are lower,generally leading to more stable foils. Foils with high formationreaction temperatures are generally unstable and brittle and thereforeare dangerous and difficult to use. Brittle foils, for example, willcrack easily, leading to local hot spots (through the release of elasticstrain energy and friction) that ignite the foil. Cutting such brittlefoils (e.g., for specific joint sizes) is very difficult to do as theyare more likely to crack into unusable pieces or igniting during thecutting process. Freestanding thick foils offer the advantage ofovercoming problems associated with thermal shock and densificationproblems that have presented obstacles in known processes. Bothphenomena relate to rapid changes in the dimensions of the foils. Onreacting, the foils will heat rapidly and will try to expand beyond thesubstrate that constrains them. This leads to a thermal shock and foilsthat are deposited on substrates can debond, thereby causinginconsistent and less effective bonding. As the reaction proceeds, thefoils will also densify, due to the change in chemical bond. Thisdensification, can also cause debonding from a substrate andinconsistent and ineffective bonding. By making the foil freestanding inaccordance with a preferred embodiment of the invention, no debondingoccurs, the foil is easily manipulated and handled, and thus thereactive foil is made available to a greater variety of applications.

In accordance with a preferred embodiment, the thicker reactive foilsare on the order of 50 μm to 1 cm thick. Although a number of differentsystems may be employed to create the thick freestanding reactive foils,a unique process in selecting the fabrication conditions for theemployed system should be carefully selected. For example, depositionconditions such as sputter gas and substrate temperature areadvantageously chosen so that stresses remain sufficiently low in thefilms or foil as they are deposited in the system. Since the stress inthe film times its thickness scales with the driving force fordelamination, the product of stress and foil thickness should be keptbelow 1000 N/m. Stresses often arise in the films during the fabricationprocess. As the films grow thicker, they are more likely to peel offtheir substrates or crack their substrates than thinner films, therebyruining the final foil production. By characterizing the stresses in thefilms and selecting conditions to minimize the stresses, the fabricationprocess can be completed without the premature peeling off of the foilor the cracking of the substrate.

In an alternative embodiment, openings in a reactive foil areintentionally designed in the foil structure. These openings are ofparticular use in facilitating and enhancing joining applications.

The foil may be initially fabricated, for example, with one or moreopenings or perforations 22 through the foil structure, as shown in FIG.4. Preferably the openings are formed in a periodic pattern, such as arectangular array, across the foil area. Any known method may beemployed to create openings. For example, sputter depositing of the foil14 on a removable substrate with patterned holes may be used. Theopenings may also be formed by depositing the foil 14 onto a substrate,depositing photoresist on the foil, patterning the photoresist withphotolithography, and then etching the underlying foil through thepatterned holes. A further exemplary technique involves physicallypunching holes in foil 14. Preferably the openings have effectivediameters in the range of 10–10,000 micrometers. (The effective diameterof a non-circular opening is the diameter of a circular opening of equalarea.)

As shown in FIG. 4, the openings in foil 14 allow joining material 12,or bulk material 10 in some circumstances, to extrude (as shown byarrows 26) through these perforations 22 upon being heated and softenedby the exothermic reaction of foil 14. Upon this extrusion, one layer ofjoining material 12, or bulk material 10, may contact and couple withanother layer 12, or bulk material 10, on the opposite side of thefreestanding foil 14. The patterned perforations 22 permit enhancedbonding of bulk materials 10 to reactive foil 14 and each other makingstronger and more consistent bonds.

FIG. 5 is a microphotograph showing two copper bodies 53, 54 bonded bysilver solder 50 that has extruded through openings, e.g. 51 in areacted foil 52.

Utilizing one or more embodiments of the invention, a number ofdifferent applications can now be performed more effectively andefficiently. For example, metallic glass bulk materials can now bejoined, where the end product is a single structure made up solely ofmetallic glass, including the bond and reacted foil layer. It is alsonow possible to join bulk materials with very different chemicalcompositions, thermal properties, and other physical properties, thathistorically presented many difficulties in bonding. Semiconductor ormicroelectronic devices may be bonded to circuit boards or otherstructures, and at the same time, multiple leads may be created that areintricately associated with the devices. Semiconductor andmicroelectronic devices may also be sealed hermetically.

These joining applications are enhanced by the invention in thatpotential for heat damage, normally associated with such applications assoldering, brazing, and welding, is avoided or at least minimized.

Moreover, utilizing embodiments of the invention, the bulk materialsbeing joined may be freestanding. This means that prior to the actualjoining of the bulk materials, the individual bulk substrates do notneed any braze layer deposited directly upon them. Additionally, thebulk substrates do not necessarily require any pre-bonding of thereactive foil or other pre-treatment. The bulk materials involved maysimply be held securely to either a freestanding braze layer or thefreestanding reactive foil at the time of bonding for a strong andpermanent joint to be created.

Embodiments of the invention allow bonding at least one bulk that is ametallic glass. No braze need be associated with that bulk in thejoining process. This is because the reactive foil may be designed tobond directly with a metallic glass upon reaction. To accomplish thisjoining process, the reactive foil can itself react to form a metallicglass.

Embodiments of the invention further allow for superior bonding when thebulk materials include microchips or semiconductor devices. In thebonding of semiconductor devices to a substrate such as a circuit board,potential for damage to the device is a factor that must be taken intoconsideration. By using a freestanding reactive foil to join such asemiconductor device to a substrate, little heat is generated that canbe damaging to the device or to adjacent components. The semiconductordevices may be situated on the substrate with greater freedom and ease.As described below, specific foil compositions, such as Ni/Al orMonel/Al, may be utilized. Foils of such composition are not only fareasier to handle than those of the past, but the combination of Ni, Cuand Al enables freestanding foils to have a high thermal and electricalconductivity.

When bonding is directed to bulk materials such as semiconductordevices, the reactive foil may have composition patterning properties.The embodiments allow the fabrication of alternating adjacentelectrically insulating and conducting regions in the final reactedfoil, thereby allowing a multitude of leads to be bonded andelectrically isolated with a single reaction.

In a preferred embodiment of the invention, less energy is required toperform a joining application utilizing reactive foils. Functionallygraded layers as joining material allow for control over meltingtemperatures through selection of their composite materials.Functionally graded layers may be utilized, for example, because theirmelting temperature may be controlled. Ni—B films used as joiningmaterial allow for low temperature melting where the melting temperaturebegins at a relatively low temperature and elevates as B diffuses out ofNi, resulting in a final material with a relatively high melting point.By requiring less energy from the foil reaction, the overall heatapplied to the total structure to be bonded can be reduced, therebyminimizing damage to the materials to be bonded due to the foilreaction.

In another embodiment, one may include layers of reactive multilayerbraze within the reactive multilayer foil. For example, in a foilcomprising reactive layers of Al and reactive layers of Ti, Zr or Hfalloys, one may include one or more layers comprising Cu or Ni alloys.The Cu or Ni alloys can react with the Al, Ti, Zr or Hf layers to form areactive braze that can act as a joining material. The reactivemultilayer braze would provide an energy source as the layers mix andform the joining material, in addition to the energy provided by thereactive foil. The combination of reactive multilayer foil and reactivemultilayer brazes permits the use of reactive brazes that may notself-propagate without the foil.

In bonding applications where the reaction products of the reactive foildo not themselves act as a joining material, it is advantageous toprovide a joining material (braze or solder) that the foil will melt orsoften and that will adhere to the bodies to be bonded together. Thejoining material can be conveniently provided in a layered bondingstructure comprising the reactive multilayer foil and one or more layersof the joining material. Preferred joining materials are amorphousmaterials such as metallic glass alloys.

In such applications, the method of bonding a first body to a secondbody comprises disposing between the first body and the second body, atleast one layer of joining material and a reactive multilayer foil. Thebodies are pressed together against the joining material and the foil isignited to melt or soften the joining material.

It is advantageous that the heated joining material be able to flowthrough the reacted foil so that the first body is bonded to the secondby the joining material. This can be facilitated by providing aplurality of openings in the foil through which the nested joiningmaterial can flow. Such flow through can also be facilitated byproviding a reactive foil that shrinks in volume after ignition.Shrinkage in volume leads to cracks through which the heated joiningmaterial can flow. Advantageously the foil shrinks in volume by at least10%. The cracking can be facilitated by perforating or scoring the foilor by putting the foil under tensile stress. Flow of the joiningmaterial through the foil can also be facilitated by preheating thejoining material before ignition to enhance the joining material flow.

When the reacted foil is not an effective joining material, it is alsoadvantageous that as much as possible of the foil reaction products beextruded from the joint between the first and second bodies afterignition. Such extrusion out of the joint can be facilitated byincreasing the pressure between the two bodies (to pressures in excessof about 10 MPA). Extrusion of the reacted foil can also be facilitatedby the use of amorphous joining materials that soften and flow withrelatively high viscosity upon heating above their glass transitiontemperature. Such amorphous materials that gradually soften aredistinguishable from crystalline materials that have sharply definedmelting points. The amorphous material softens gradually withtemperature and exhibits a similar gradual decrease in viscosity withtemperature. The crystalline material has an abrupt decrease inviscosity upon melting. (If a joining material with sharply definedmelting points is used, it is advantageous to disperse non-meltingparticles within the joining material to increase its viscosity whenmolten.) A higher viscosity in the heated joining material combined withthe pressure applied to the bodies during joining ejects a greaterquantity of foil reaction product from the joint interface. The higherviscosity joining material transfers shear stresses to the reactionproduct, effectively dragging it out of the joint interface. This flowof joining material and ejection of reaction product is believedenhanced by using thicker foils (≧100 micrometers) and/or by the use ofmore energetic foils (≧90 J/cm²). Such thicker, energetic foils havebeen found to produce stronger bonds. The preferred amorphous materialsare amorphous metallic alloys and metallic glasses or alloys that can beamorphized (turned amorphous) by rapid heating and cooling.

Also very useful in bonding applications are quasicrystallinematerials—materials that are solid with long range atomic order asdemonstrated by an essentially discrete diffraction pattern, but whichare not periodic on the atomic scale. Particularly useful for bondingare reactive foils comprising alternate layers of alloys that, afterreaction and cooling, are fully or partially quasicrystalline. Forexample combinations of alloys comprising Ni or Cu, alloys that compriseTi, Zr or Hf and alloys that comprise Al can react to form amorphousphases at a high cooling rate and stable intermetallic phases at a slowcooling rate. But at intermediate cooling rates they can formquasicrystalline phases embedded in a metallic glass matrix. Such atwo-phase structure can be stronger than single-phase metallic glass butnonetheless retain the good wetting characteristics of metallic glassfor joining.

EXAMPLES

The invention may now be more clearly understood by consideration of thefollowing specific examples:

Example 1

Reactive foils of Al and Ni are formed by cold rolling many 5 μm sheetsof Ni and Al that are stacked together. FIG. 6 schematically illustratesfabrication of the foil 60 by passage of the stack 61 between rollers62A and 62B. The sheets can be cold-rolled several times until thelayers are reduced to the desired thickness.

Example 2

Instead of utilizing foils comprised of multilayers of uniformthickness, a composite foil is used, in which nanolaminate reactivemultilayers are deposited onto reactive microlaminate foils. Asillustrated in FIG. 7 certain sections of layers 70 within the reactivefoil 71 will be of a nanoscale (nanolaminate), while other sections 72will be of micron-thick layers (microlaminate). The nanolaminate, asdescribed above, will react easily and the reaction, once started, willself-propagate along the length of the foil without being quenched bythe melting of the surrounding braze layers or bulk components. Thus,the nanolaminate can be viewed as an igniter for the microlaminate. Thesection 72 with microscale layers may not be able to sustain aself-propagating reaction at room temperature, but when heated byadjacent nanolaminate sections 70, it will sustain such a reaction. Thefoil can comprise alternate layers of Al and Ni.

Example 3

In fabricating these composite foils, sheets of Al and Ni are rolled toform the microlaminate section and then a nanolaminate foil is vapordeposited onto either side of this microlaminate structure. Fabricationmay also be performed through vapor deposition of the full compositewith the microlaminate layers deposited at much higher rates withoutigniting the foil or causing unacceptable intermixing between thealternating layers during deposition.

Example 4

A reactive multilayer braze is formed that is similar to the reactivefoils described above, which reacts to form a metallic glass. Thismultilayer braze gives off heat upon a reaction of its alternatinglayers. Through a careful selection of reactants that are know to begood glass formers, the braze will form an amorphous final product uponreaction, similar to those in commercial use and to the foils describedabove. The heat generated by the reacting braze layers reduces theamount of reactive foil required for joining.

Example 5

Certain compositions of foil 14 may react to form amorphous alloys(metallic glass). Those foils may be combinations of layers of alloysthat comprise Ni or Cu, alloys that comprise Ti, Zr, or Hf, and alloysthat comprise Al as such will react to form metallic glass. When usingsuch foils, certain properties may be attained. Metallic glasses havevery good wetting capabilities. The braze layer may be excluded whenusing such a foil to join bulk metallic glass and in such acircumstance, once the foil reacts and is joined with the metallicglass, a single bulk metallic glass may be produced.

Example 6

A semiconductor or microelectronic device is joined to a substrate suchas a printed circuit board using a reactive multi-layer foil. FIG. 8schematically illustrates the joining arrangement wherein the reactivefoil 80 is sandwiched between solder layers 81A and 81B, and thesandwich is disposed between the contact lead 82 for the device 83 andthe contact surface 84 of the board.

Example 7

A patterned reactive foil is designed so that some sections react toform electrically conductive regions and other sections formnon-conductive regions.

FIGS. 9A and 9B schematically illustrate the concept. FIG. 9A shows thefoil 90 before reaction. FIG. 9B is after the reaction. Regions 91,comprising alternate layers of Al and Ni, react to form conductiveregions 95. Regions 92, comprise insulators, such as SiO₂ or siliconnitride, or alternate layers that react to form non-conductive regions.

It is contemplated that in use, regions 91 would be registered betweencontacts above and below the foil 90 to be electrically connectedthrough the regions 95 after the reaction.

It can now be seen that one aspect of the invention is a method ofmaking a reactive multilayer foil composed of a plurality of alternatinglayers that can react exothermically. The method comprises the steps ofproviding a substrate, vapor depositing the alternating layers on thesubstrate to form the multilayer foil, and separating the multilayerfoil from the substrate. Advantageously the substrate has sufficientadherence to the deposited layers to retain the layers during depositionbut insufficient adherence to prevent removal of the multilayer foilafter deposition. As an example, the layers can comprise one or morelayers of aluminum deposited in contact with a silicon substrate.Alternatively, the substrate can include a coating of release materialor an adhesion material to achieve the proper level of adherence.

One approach for separating the multilayer foil from the substrate is toprovide a substrate with a sacrificial layer (or make the entiresubstrate a sacrificial layer) that can be etched or peeled away fromthe foil after deposition. Exemplary materials for a sacrificial layerinclude copper, brass and photoresist.

The vapor depositing of the layers is preferably by physical vapordeposition such as by magnetron sputtering or electron beam evaporation.Advantageously the substrate is cooled during the vapor depositing toreduce intermixing of the alternating layers, to reduce energy lossesand to reduce stresses in the deposited layers. Advantageously thelayers are deposited to form a multilayer foil having a thickness in therange 50 μm–1 cm. Foils thus made with a thickness in the range 10 μm to1 cm can be used as freestanding foils.

Another aspect of the invention is a method of bonding a first body to asecond body comprising the steps of providing a freestanding reactivemultilayer foil, pressing the bodies together against the foil andigniting the reactive foil. The ignited foil can melt material of thebodies or melt or soften an associated joining material layer to jointhe bodies together. Alternatively, the reaction product of the layerscan itself be the joining material. One or both of the bodies can besemiconductor or microelectronic devices. The method is particularlyadvantageous for joining bodies having coefficients of thermalexpansion, which differ by 1 μm/m/° C. or more.

In an alternative embodiment, a reactive multilayer foil includes aplurality of openings through the thickness of the foil. The openingsare preferably periodic over the foil area. These openings can be leftunfilled or they can be filled with joining materials, propellants, orother materials that will change or react on heating when the reactivefoil is ignited.

Such apertured foils can be made by providing a substrate having asurface including a plurality of preformed openings, bumps or particlesof thickness (or depth) comparable to or larger than the thickness ofthe multilayer foil to be deposited, depositing the reactive multilayerfoil, and separating the resulting apertured multilayer foil from thesubstrate.

Alternatively, a reactive multilayer foil can be deposited on asubstrate, patterned by a removable masking layer, and etched to form aplurality of holes. The apertured foil can then be removed from thesubstrate. Yet further in the alternative, a continuous foil can beformed and holes can be formed in the continuous foil by mechanicalpressing.

The apertured foils have an important application in bonding. A reactivefoil perforated by a plurality of openings is disposed between a firstand a second body. If the body material is not meltable by the foil, aseparate layer or coating of joining material is also disposed betweenthe bodies. The bodies are pressed together against the foil (andjoining material) and the foil is ignited to melt or soften the joiningmaterial. The joining material flows within and through the openings inthe foil to join the bodies. This approach produces a characteristicjoint with ductility enhancing bridges through the openings. It isespecially advantageous where one or both bodies are semiconductor ormicroelectronic devices or where the devices have CTEs that differ bymore than 1 μm/m/° C.

A third type of novel reactive foil is a composite reactive multilayerfoil in which the individual layers in the foil differ in thickness orin composition, on moving across the total thickness of the foil, toachieve advantageous results. One exemplary composite reactivemultilayer foil comprises a first section with a plurality of relativelythick reactive layers, e.g. 1 μm to 10 μm, stacked on a second sectionwith a plurality of thinner reactive layers (e.g. 1–1000 nm). Thesection with the thinner reactive layers ignites more rapidly than wouldthe section with the thicker reactive layers. But as ignition spreadsacross the thinner section, it ignites the thicker section to produce amore uniform ignition and higher heat. Similar results can be achievedby variation of the foil composition in the thickness direction.Compositional variations can provide one set of layers whose reactionproduct provides joining material and another set of more reactivelayers for igniting the first set. Compositional variations can beachieved, for example, by varying the process parameters in vapordepositing in accordance with techniques well known in the art.

A fourth type of novel reactive foil has a major surface area composedof at least two different regions: one or more first regions which willreact to form electrically conductive material and one or more secondregions which are non-conductive. Such foils are particularly useful inconnecting semiconductor device electrical contacts to a substratehaving receiving contacts. A foil can be disposed between the device andthe substrate with the device contacts, the contacts of the substrateand the first regions of the foil all in registration. The device andsubstrate are then pressed against the foil, and the foil is ignited tobond the device to the substrate with the respective contactsconductively connected and the other regions non-conductively bonded.

While preferred embodiments of the invention have been described andillustrated, it should be apparent that many modifications to theembodiments and implementations of the invention can be made withoutdeparting from the spirit or scope of the invention. While theillustrated embodiments have been described generically referring to thejoining of bulk materials, it should be readily apparent that anymaterials that are to be coupled (permanently or temporarily) togetherthrough soldering, brazing, welding or other known technique can becoupled together utilizing the invention. Materials such as metallicglasses (e.g., amorphous metal), metals (e.g., Cu) and alloys (e.g.,stainless steel), polymers, ceramics (e.g. SiC), composites,semiconductors, and numerous others in various combinations. The scopemade available as a direct result of the advantages derived by joiningmaterials utilizing the invention range from large scale bonding of SiCarmor to Ti—Al—V tank bodies, or the bonding of carbide coatings to toolbits, to microscopic bonding of microchips to circuit boards on a nanoor microscale.

The stimulus used to initiate the self-sustaining reaction in thereactive foils of the preferred embodiments may be any form of energysuch as the impact from a sharp stylus, spark from an electrical source,heat from a filament, radiation from a laser, etc. Although theillustrated embodiments have been described as applied in an environmentof air at room temperature, it should be readily apparent that theinvention may be practiced in other environments including vacuum,argon, water, etc.

It should be readily apparent that the quantitative data (e.g., reactionvelocity, peak temperature, heating rate, etc.) of particularembodiments may easily be modified by varying elements of the reaction(e.g., varying composition of materials A or B, thickness of layers,total thickness of foil, or braze layer composition/thickness).

Although the embodiments specifically illustrated herein depict joiningmaterials in the form of two sheets forming a sandwich around a reactivefoil (as shown, for example, by sheets 12 and foil 14 in FIGS. 2 and 3),it should be apparent that any number of sheets (or other structures) ofjoining materials may be used, including a single layer wrapped aroundreactive foil 14 or joining materials attached to the bulk components.In accordance with a preferred embodiment, no layer of joining materialat all may also be used. For example, metallic glass bulk material,metallic glass reactive foils, or both may be used in joiningapplications without the use of joining material (e.g., braze).

Moreover, although the illustrated embodiments have only utilized twodifferent materials A/B as alternating layers in a reactive foil, itshould be apparent that any number of material layers can be utilized toform a reactive foil in accordance with the invention.

In addition, many of the preferred embodiments disclosed herein (e.g.,patterning foils, perforations in the foil, etc.) make particular use offreestanding foils, it should be readily apparent, however, that theseembodiments and other aspects of the invention may be implementedwithout use of freestanding foils. Furthermore, it should be readilyapparent that the intentionally designed openings in the reactive foilsurface may penetrate through any number of layers in the foil, althoughit is preferred that the entire foil structure be penetrated as shown,for example, in FIG. 5. The openings, while depicted in FIG. 4 ascircle-shaped holes 22, may be any single (or combination) of shapesforming one or more patterned structures on the reactive foil. Theopenings may be formed vertically in the direction normal to the layersof the reactive foil, or be formed at one or more angles through thelayers of the foil.

Thus numerous and varied other arrangements can be made by those skilledin the art without departing from the spirit and scope of the invention.

1. A layered structure for bonding together two bodies comprising afreestanding reactive multilayer foil and a layer of joining material,wherein a product of stress in the foil and the foil thickness is lessthan or equal to 1000 N/m.
 2. A layered structure for bonding togethertwo bodies comprising a reactive multilayer foil and a layer of joiningmaterial, wherein the reactive multilayer foil is scored or perforatedto facilitate cracking after ignition.
 3. A layered structure forbonding together two bodies comprising a reactive multilayer foil and alayer of joining material, wherein the reactive multilayer foil has aplurality of openings for the passage of the joining material afterheating.
 4. A layered structure for bonding together two bodiescomprising a reactive multilayer foil and a layer of joining material,wherein the joining material comprises an amorphous material.
 5. Alayered structure for bonding together two bodies comprising a reactivemultilayer foil and a layer of joining material, wherein the joiningmaterial comprises a metallic glass.
 6. A layered structure for bondingtogether two bodies comprising a reactive multilayer foil and a layer ofjoining material, wherein the joining material comprises a crystallinemetallic material that cools to a material comprising amorphous materialafter heating by ignition of the reactive foil.
 7. A layered structurefor bonding together two bodies comprising a reactive multilayer foiland a layer of joining material, wherein the joining material comprisesa crystalline metallic material that cools to a fully or partiallyquasicrystalline state after heating by the reactive foil.
 8. A methodof bonding a first body to a second body comprising the steps of:disposing between the first body and the second body, a freestandingreactive multilayer foil, wherein at least one of the two bodiescomprises a metallic glass; pressing the bodies together against thefoil; and igniting the reactive foil.
 9. A method of bonding a firstbody to a second body comprising the steps of: disposing between thefirst body and the second body, a reactive multilayer foil and at leastone joining material, the reactive multilayer foil having a plurality ofopenings through the thickness of the foil, wherein at least one of thetwo bodies comprises a metallic glass; pressing the bodies togetheragainst the foil and the joining material; and igniting the reactivefoil to heat the joining material and permit the melted or softenedjoining material to flow through the openings to join the first andsecond bodies.
 10. A method for bonding a first body to a second bodycomprising the steps of: disposing between the first body and the secondbody, a reactive multilayer foil comprising a plurality of successiveexothermic reactive layers that react to form a joining material;pressing the bodies together against the foil; and igniting the foil.11. The method of claim 10 wherein at least one of the first and secondbodies comprise metallic glass.
 12. The method of claim 10 wherein thereactive multilayer foil comprises alternate layers of alloys that,after reaction and cooling, comprise amorphous material.
 13. The methodof claim 10 wherein the reactive multilayer foil comprises alternatelayers that, after reaction and cooling, are fully or partiallyquasicrystalline.
 14. The method of claim 10 wherein the reactivemultilayer foil comprises alternate layers of an alloy comprising Ni orCu, an alloy comprising Ti, Zr, or Hf, and an alloy containing Al.
 15. Amethod of bonding a first body to a second comprising the steps of:disposing between the first body and the second body, a freestandingreactive multilayer foil and at least one layer of joining material,wherein the joining material comprises a metallic glass; pressing thebodies together against the foil and joining material; and igniting thereactive foil to melt or soften the joining material.
 16. A method ofbonding a first body to a second body comprising the steps of: disposingbetween the first body and the second body, a reactive multilayer foiland at least one layer of joining material; pressing the bodies togetheragainst the layer of joining material and the foil; and igniting thereactive foil to melt or soften the joining material, wherein thereactive multilayer foil forms cracks through the foil after ignition topermit the heated joining material to flow through the foil.
 17. Amethod of bonding a first body to a second body comprising the steps of:disposing between the first body and the second body, a reactivemultilayer foil and at least one layer of joining material; pressing thebodies together against the layer of joining material and the foil; andigniting the reactive foil to melt or soften the joining material,wherein the reactive multilayer foil has scoring or a plurality ofopenings to facilitate cracking after ignition.
 18. A method of bondinga first body to a second body comprising the steps of: disposing betweenthe first body and the second body, a reactive multilayer foil and atleast one layer of joining material; pressing the bodies togetheragainst the layer of joining material and the foil; igniting thereactive foil to melt or soften the joining material; and placing thefoil under tensile force to facilitate cracking of the foil andextrusion out of the joint interface after ignition.
 19. A method ofbonding a first body to a second body comprising the steps of: disposingbetween the first body and the second body, a reactive multilayer foiland at least one layer of joining material; pressing the bodies togetheragainst the layer of joining material and the foil; igniting thereactive foil to melt or soften the joining material; and pressing thetwo bodies together against the joining material and the foil withsufficient pressure to extrude a portion of foil reaction products frombetween the bodies after ignition.
 20. A method of bonding a first bodyto a second body comprising the steps of: disposing between the firstbody and the second body, a reactive multilayer foil and at least onelayer of joining material; pressing the bodies together against thelayer of joining material and the foil; and igniting the reactive foilto melt or soften the joining material, wherein the joining materialwhen heated by the reactive foil has sufficient viscosity to facilitateextrusion of foil reaction products from between the bodies afterignition.
 21. A method of bonding a first body to a second bodycomprising the steps of: disposing between the first body and the secondbody, a reactive multilayer foil and at least one layer of joiningmaterial, wherein the layer of joining material includes dispersedparticles to increase the viscosity of the material when molten;pressing the bodies together against the layer of joining material andthe foil; and igniting the reactive foil to melt or soften the joiningmaterial.
 22. A method of bonding a first body to a second bodycomprising the steps of: disposing between the first body and the secondbody, a reactive multilayer foil and at least one layer of joiningmaterial; pressing the bodies together against the layer of joiningmaterial and the foil; preheating the joining material; and igniting thereactive foil to melt or soften the joining material.
 23. A method ofbonding a first body to a second body comprising the steps of: disposingbetween the first body and the second body, a reactive multilayer foiland at least one layer of joining material; pressing the bodies togetheragainst the layer of joining material and the foil; and igniting thereactive foil to melt or soften the joining material, wherein thejoining material is heated and cooled with sufficient rapidity to forman amorphous material.
 24. A method of bonding a first body to a secondbody comprising the steps of: disposing between the first body and thesecond body, a reactive multilayer foil and at least one layer ofjoining material, wherein the joining material comprises an amorphousmaterial; pressing the bodies together against the layer of joiningmaterial and the foil; and igniting the reactive foil to melt or softenthe joining material.
 25. A method of bonding a first body to a secondbody comprising the steps of: disposing between the first body and thesecond body, a reactive multilayer foil and at least one layer ofjoining material; pressing the bodies together against the layer ofjoining material and the foil, wherein the first and second bodies arepressed against the joining material and foil with a pressure greaterthan about 10 MPA; and igniting the reactive foil to melt or soften thejoining material.
 26. A method of bonding a first body to a second bodycomprising the steps of: disposing between the first body and the secondbody, a reactive multilayer foil and at least one layer of joiningmaterial, wherein the reactive foil has thickness in excess of about 100micrometers; pressing the bodies together against the layer of joiningmaterial and the foil; and igniting the reactive foil to melt or softenthe joining material.
 27. A method of bonding a first body to a secondbody comprising the steps of: disposing between the first body and thesecond body, a reactive multilayer foil and at least one layer ofjoining material, wherein the reactive foil generates an energy densitygreater than about 70 J/cm²; pressing the bodies together against thelayer of joining material and the foil; and igniting the reactive foilto melt or soften the joining material.